Enhanced Photocatalytic Activity of Hyper‐Cross‐Linked Polymers Toward Amines Oxidation Coupled with H2O2 Generation through Extending Monomer's Conjugation Degree

Visible-light-driven amines oxidation coupled with hydrogen peroxide (H₂ O₂ ) generation is a promising way to convert solar energy to chemical energy. Herein, a series of hyper-cross-linked polymers (HCPs) photocatalysts with different arenes monomers, including benzene (BE), diphenyl (DP), p-terphenyl (TP), or p-quaterphenyl (QP), were synthesized by simple Friedel-Crafts alkylation reaction. Owing to the maximum monomer's conjunction degree and excellent oxygen (O₂ ) adsorption capacity, QP-HCPs exhibited highest photocatalytic activity for benzylamine oxidation coupled with H₂ O₂ generation under the irradiation of 455 nm Blue LED lamp. More than 99 % of benzylamine could be converted to N-benzylidenebenzylamine within 60 min. In addition, nearly stoichiometric H₂ O₂ was synchronously obtained with a high production rate of 9.3 mmol g_cat ^-1 h^-1 . Our work not only demonstrated that the photocatalytic activity of HCPs photocatalysts significantly depends on monomer's conjunction degree, but also provided a new strategy for converting solar energy to chemical energy.